CN103467912B - One has high-flexibility composition epoxy resin - Google Patents
One has high-flexibility composition epoxy resin Download PDFInfo
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- CN103467912B CN103467912B CN201310343702.5A CN201310343702A CN103467912B CN 103467912 B CN103467912 B CN 103467912B CN 201310343702 A CN201310343702 A CN 201310343702A CN 103467912 B CN103467912 B CN 103467912B
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- butyral acetal
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Abstract
The invention provides one and there is high-flexibility composition epoxy resin, can be used for electronic package material and art of powder coatings.This composition epoxy resin comprises epoxy resin, polyvinyl butyral PVB, solidifying agent and other matrix materials.Wherein, epoxy resin 30 ~ 50 mass parts, polyvinyl butyral (PVB) 1 ~ 30 mass parts, solidifying agent 3 ~ 10 mass parts, curing catalyst 0.05 ~ 0.3 mass parts, mineral filler 30 ~ 60 mass parts.Composition epoxy resin involved in the present invention has inierpeneirating network structure and excellent snappiness, for electronic package material and art of powder coatings.
Description
Technical field
The invention belongs to electronic package material and art of powder coatings, relate to one and there is high-flexibility composition epoxy resin.
Background technology
Epoxy resin is one of most widely used matrix resin in polymer matrix composite, polycondensation is carried out and obtained product by having the compound of epoxy group(ing) and multi-hydroxy or polyol compound, there is excellent cohesiveness, chemical resistance, electrical insulation properties, mechanical property, and be easy to processing, shrinking percentage is low, coefficient of linear expansion is little and the advantage such as with low cost, is widely used in electronic package material and art of powder coatings.
But because the toughness of pure epoxy resin is not enough, cause curing material crisp, the defect such as easily to crack, cannot be used for the encapsulation that cold-hot impact requires higher electronic devices and components, its application receives larger restriction.Based on this, Chinese scholars has carried out a large amount of study on the modification work to epoxy resin, summarize many method for toughening: expanded polystyrene veneer is epoxy resin toughened, liquid crystalline polymers is epoxy resin toughened as adopted, core-shell Polymer toughening epoxy resin etc., and ipn technology is applied to the toughness reinforcing of epoxy resin by the present invention.Interpenetrating polymer networks (IPN) is blend polymer or the polymer alloy of a class uniqueness of being tangled by network interpenetrating by two or more polymkeric substance and being formed.IPN is distinctive forces mutual tolerance interaction energy to make two kinds of performance differences very large or have the stable combination of the polymer formation of difference in functionality, thus realizes performance complement between component; The structural form features such as simultaneously the special cells shape structure of IPN, interface IPN, two-phase be continuous, make again them in performance or functionally have special synergy.Preparation method, it is close to graft copolymerization blending method, has inorganic chemistry to take into consideration from alternate, then close to mechanical blending method, therefore, can IPN be considered as with chemical method realize mechanical blend.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, provide one to have high-flexibility composition epoxy resin, to meet electronic package material to the requirement of resistance to sudden cooling and the drag impact property improving powder coating.
The technical scheme that the present invention realizes object is:
One has high-flexibility composition epoxy resin, and it forms component and mass fraction is respectively:
And described epoxy resin softening temperature is less than <140 DEG C, epoxy equivalent (weight) 160 ~ 2000g/eq.
And described epoxy resin is diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin or bisphenol A type epoxy resin.
And described polyvinyl butyral acetal: polyvinyl alcohol hydroxy radical content scope is 11 ~ 27wt%, polyvinyl butyral acetal base content range is 69 ~ 88wt%, and vinyl acetate between to for plastic base content range is 1 ~ 4wt%, and glass transition temperature Tg scope is 60 ~ 70 DEG C.
And, described polyvinyl butyral acetal PVB addition manner: directly add as component or first and epoxy resin and filler carry out pre-treatment after add again.
And pretreatment technology is as follows:
Pretreatment process: epoxy resin, polyvinyl butyral acetal and filler carry out melting mixing in proportion and extrude, extrusion temperature 70 ~ 150 DEG C, forcing machine rotating speed 1500 ~ 3000r/min, rate of feeding 900 ~ 2400r/min, adding proportion: the mass ratio of epoxy resin, polyvinyl butyral acetal and filler three is: (1 ~ 5): (1 ~ 3): (0 ~ 3).
And described solidifying agent is at least one in organic acid or acid anhydride type curing agent, phenols curing agent, polynary amine curing agent, imidazoles.
And described curing catalyst is any one in imidazoles, imidazolines, trialkyl phosphorus, quaternary ammonium salt, quaternary phosphine salt, organic ureas.
And described mineral filler is at least one in silica flour, talcum powder, calcium carbonate, mica powder, and median size is between 1 ~ 50 micron.
Prepare a method with high-flexibility composition epoxy resin, specific as follows:
Epoxy resin, polyvinyl butyral acetal, solidifying agent, curing catalyst and mineral filler are mixed by mass fraction proportioning, the time of mixing is 5 ~ 20min, rotating speed 500 ~ 1000r/min; Then melting mixing is extruded, then carries out pulverizing and sieving obtaining described composition epoxy resin.
Advantage of the present invention and beneficial effect as follows:
(1) the polyvinyl butyral acetal PVB and epoxy resin with high toughening effect are carried out physical blending by the present invention, obtained have high-flexibility epoxy resin, be used further to composition epoxy resin, obtain and there is high flexile epoxy resin combination, this composition epoxy resin is used for electronic package material, the cold-hot impact of electronic package material can be increased substantially, for art of powder coatings, the drag impact property of coating can be increased substantially.
(2) the addition manner of component polyvinyl butyral acetal PVB of the present invention is various, both can directly add, also can carry out pre-treatment with epoxy resin and filler to add again, through pretreated polyvinyl butyral acetal PVB, can mix with other components better, the inierpeneirating network structure formed is finer and close, thus improves the snappiness of composition further.
(3) composition epoxy resin preparation method of the present invention is simple, and condition is easy to control, administration measure, and non-volatile thing in process of production, the feature of environmental protection is strong.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
The polyvinyl butyral acetal PVB(I that the present invention uses), polyvinyl butyral acetal PVB(II) in I, II uses for mark is clear, do not have particular meaning.
Embodiment 1:
One has high-flexibility composition epoxy resin, and concrete component and consumption are in table 1, and preparation method is as follows:
By epoxy resin (E-12), polyvinyl butyral acetal PVB(I), solidifying agent, curing catalyst and mineral filler mix by mass fraction proportioning, the time of mixing is 5 ~ 20min, rotating speed 500 ~ 1000r/min; Then melting mixing is extruded (extrusion temperature 70 ~ 150 DEG C, forcing machine rotating speed 1500 ~ 3000r/min, rate of feeding 900 ~ 2400r/min), then carries out pulverizing and sieving obtaining described composition epoxy resin.
Wherein, polyvinyl butyral acetal PVB(I) design parameter is: polyvinyl alcohol hydroxy radical content is 21wt%, and polyvinyl butyral acetal base content range is 78wt%, and vinyl acetate between to for plastic base content range is 1wt%, and glass transition temperature Tg scope is 63 DEG C.
Embodiment 2:
One has high-flexibility composition epoxy resin, and concrete component and consumption are in table 1, and preparation method is as follows:
By epoxy resin (E-12), polyvinyl butyral acetal PVB(II), solidifying agent, curing catalyst and mineral filler mix by mass fraction proportioning, the time of mixing is 5 ~ 20min, rotating speed 500 ~ 1000r/min; Then melting mixing is extruded (extrusion temperature 70 ~ 150 DEG C, forcing machine rotating speed 1500 ~ 3000r/min, rate of feeding 900 ~ 2400r/min), then carries out pulverizing and sieving obtaining described composition epoxy resin.
Wherein, polyvinyl butyral acetal PVB(II) design parameter is: polyvinyl alcohol hydroxy radical content is 25wt%, and polyvinyl butyral acetal base content range is 74wt%, and vinyl acetate between to for plastic base content range is 1wt%, and glass transition temperature Tg scope is 61 DEG C.
Comparative example:
Epoxy resin (E-12), solidifying agent, curing catalyst and mineral filler are carried out pre-mixing by mass fraction proportioning, and the time of pre-mixing is 5 ~ 20min, rotating speed 500 ~ 1000r/min; Then melting mixing is extruded (extrusion temperature 70 ~ 150 DEG C, forcing machine rotating speed 1500 ~ 3000r/min, rate of feeding 900 ~ 2400r/min), then carries out pulverizing and sieving.
The proportioning of three groups of example composition components and the performance of coating curing thing as shown in table 1.
The performance of table 1 epoxy composite component proportion and coating curing thing
| Component | Unit | Reference example | Embodiment 1 | Embodiment 2 |
| Epoxy resin (E-12) | g | 50 | 50 | 40 |
| Polyvinyl butyral acetal PVB(I) | g | —— | 10 | —— |
| Polyvinyl butyral acetal PVB(II) | g | —— | —— | 10 |
| Dyhard RU 100 | g | 3.9 | 3.9 | 3.9 |
| Imidazoles | g | 0.10 | 0.10 | 0.10 |
| Silicon-dioxide | g | 50 | 50 | 40 |
| Cold-hot impact | Individual | 20 | 95 | 100 |
Form components description as follows:
Described epoxy resin requires that softening temperature is less than <140 DEG C, epoxy equivalent (weight) 160 ~ 2000g/eq, comprises diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin, preferred bisphenol A type epoxy resin; Account for 30 ~ 50 mass parts of total composition.
Described polyvinyl butyral acetal PVB, polyvinyl alcohol hydroxy radical content scope is 5 ~ 38wt%, and polyvinyl butyral acetal base content range is 69 ~ 88wt%, and vinyl acetate between to for plastic base content range is 1 ~ 4wt%, and glass transition temperature Tg scope is 60 ~ 70 DEG C; Account for 1 ~ 30 mass parts of total composition.
Described solidifying agent is at least one in organic acid or acid anhydride type curing agent, phenols curing agent, polynary amine curing agent, imidazoles, accounts for 3 ~ 10 mass parts of total composition.
Involved curing catalyst is any one in imidazoles, imidazolines, trialkyl phosphorus, quaternary ammonium salt, quaternary phosphine salt, organic ureas, accounts for 0.05 ~ 0.3 mass parts of total composition.
Involved mineral filler is at least one in silica flour, talcum powder, calcium carbonate, mica powder.The addition of this mineral filler accounts for 30 ~ 60 mass parts of composition gross weight.
Testing performance index method involved in the present invention is as follows:
(1) the mensuration of epoxy equivalent (weight): according to ISO3001-1978 " mensuration of plastics-epoxy compounds-epoxy equivalent (weight) ";
(2) softening temperature: measure according to the method described in GB12007.6-89 " epoxy resin softening point measurement method ring and ball method ";
(3) cold-hot impact
That the destructive test that ftractures is occurred in the environment of high temperature and low temperature successively alternation to the coating of electronic devices and components; The design temperature of high temperature and time length all can require to set according to difference, and low temperature is also like this; The resistance to high temperature of coating and a low temperature, be called a circulation; The cycle index of coating before cracking is more, and its cold-hot impact property is better.
Cold-hot impact condition involved in the present invention: high temperature is set as+125 DEG C, and low temperature is set as-55 DEG C.
Claims (1)
1. there is a high-flexibility composition epoxy resin, it is characterized in that: preparation method is as follows:
Epoxy resin E-12, polyvinyl butyral acetal PVB, solidifying agent, curing catalyst and mineral filler are mixed by mass fraction proportioning, the time of mixing is 5 ~ 20min, rotating speed 500 ~ 1000r/min; Then melting mixing is extruded, extrusion temperature 70 ~ 150 DEG C, forcing machine rotating speed 1500 ~ 3000r/min, rate of feeding 900 ~ 2400r/min, then carries out pulverizing and sieving obtaining described composition epoxy resin;
Scheme one: there is high-flexibility composition epoxy resin component as follows:
Scheme two: there is high-flexibility composition epoxy resin component as follows:
Described polyvinyl butyral acetal PVB (I) design parameter is: polyvinyl alcohol hydroxy radical content is 21wt%, and polyvinyl butyral acetal base content range is 78wt%, and vinyl acetate between to for plastic base content range is 1wt%, and glass transition temperature Tg scope is 63 DEG C;
Described polyvinyl butyral acetal PVB (II) design parameter is: polyvinyl alcohol hydroxy radical content is 25wt%, and polyvinyl butyral acetal base content range is 74wt%, and vinyl acetate between to for plastic base content range is 1wt%, and glass transition temperature Tg scope is 61 DEG C.
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| CN201310343702.5A CN103467912B (en) | 2013-08-08 | 2013-08-08 | One has high-flexibility composition epoxy resin |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104479289A (en) * | 2014-11-21 | 2015-04-01 | 芜湖市宝艺游乐科技设备有限公司 | Corrosion-resistant epoxy resin composite material and preparation method thereof |
| WO2016114317A1 (en) | 2015-01-16 | 2016-07-21 | Jnc株式会社 | Composition for forming adhesive layer, adhesive layer, manufacturing method for adhesive layer, composite material, sheet, heat dissipation member, electronic device, battery, capacitor, automobile component, and machine mechanism component |
| CN105733341A (en) * | 2016-03-03 | 2016-07-06 | 浙江久立泰祜涂层技术有限公司 | Organic modified filler for epoxy powder and preparation method for organic modified filler |
| CN106046780B (en) * | 2016-06-03 | 2018-09-25 | 中蓝晨光化工研究设计院有限公司 | Introducing has bullet resistant material of thermosetting epoxy resin and preparation method thereof |
| CN107915936B (en) * | 2016-10-07 | 2021-02-19 | 捷恩智株式会社 | Composite particle and method for producing same |
| CN106633646B (en) * | 2016-12-01 | 2019-05-31 | 陕西生益科技有限公司 | A kind of resin combination and its application |
| CN110093089A (en) * | 2019-05-21 | 2019-08-06 | 湖北来斯化工新材料有限公司 | A kind of warping resistance type fire-proof powdery paint and preparation method thereof |
| CN110373092A (en) * | 2019-08-17 | 2019-10-25 | 烟台爱丽德新材料有限公司 | A kind of heat distribution pipeline inner wall anti-corrosive powdery paints and preparation method thereof |
| CN111234751A (en) * | 2020-03-27 | 2020-06-05 | 四川东材科技集团股份有限公司 | High-strength cracking-resistant liquid pouring sealant and preparation method thereof |
| CN112480778B (en) * | 2020-11-03 | 2021-12-07 | 洛阳双瑞防腐工程技术有限公司 | Epoxy powder coating for inner wall of drinking water pipeline and preparation method thereof |
| CN114479354B (en) * | 2022-01-24 | 2024-01-05 | 东莞市维斯德新材料技术有限公司 | Preparation method of porous carbon fiber/epoxy resin composite material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508866A (en) * | 2009-03-25 | 2009-08-19 | 杜邦华佳化工有限公司 | Conductive powder paint |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508866A (en) * | 2009-03-25 | 2009-08-19 | 杜邦华佳化工有限公司 | Conductive powder paint |
Non-Patent Citations (1)
| Title |
|---|
| EP/PVB半-互穿聚合物网络的动态力学谱;晏欣;《海军工程大学学报》;20011230;第13卷(第6期);第24-26页 * |
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Address after: 300300 No. 27, Jing Lu, Dongli Economic Development Zone, Dongli District, Tianjin Patentee after: Tianjin Kaihua insulation material Limited by Share Ltd Address before: 300300 No. 27, Jing Lu, Dongli Economic Development Zone, Dongli District, Tianjin Patentee before: Tianjin Kaihua Insulation Materials Co., Ltd. |
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Address after: No.27, Yijing Road, Dongli District, Tianjin Patentee after: TIANJIN KAIHUA INSULATING MATERIALS Co.,Ltd. Address before: No. 27, Yijing Road, Dongli Economic Development Zone, Dongli District, Tianjin 300300 Patentee before: Tianjin Kaihua insulation material Limited by Share Ltd. |